Polyurethane spraying system used to minimize emissions of a polyisocyanate

ABSTRACT

A polyurethane spraying system minimizes emissions of a polyisocyanate while spraying a mixture of a polyisocyanate and a resin composition onto a surface. The system includes a first reactant supply tank including the resin composition. The system also includes a second reactant supply tank including the polyisocyanate. The system further includes a non-gaseous pump that is coupled with the first and second reactant supply tanks, a mixing apparatus that is coupled with the first and second reactant supply tanks for mixing the resin composition and the polyisocyanate prior to spraying, and a particular spray nozzle that is coupled with the mixing apparatus. The polyurethane spraying system produces less than 50 parts of the polyisocyanate per one billion parts of air according to the NIOSH 5521 Impingement Method while spraying the mixture onto the surface.

RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No.12/877,411, filed on Sep. 8, 2010, which claims priority to and all thebenefits of U.S. Provisional Patent Application Ser. No. 61/240,513,filed on Sep. 8, 2009, the entire specifications of which are expresslyincorporated herein by reference.

FIELD OF THE DISCLOSURE

The present disclosure generally relates to polyurethane spraying systemused to minimize emissions of a polyisocyanate. More specifically, thesystem utilizes particular chemistry and a non-gaseous pump to spray amixture of a polyisocyanate and a resin composition onto a surface.

DESCRIPTION OF THE RELATED ART

It is well known in the art that various hydrofluorocarbons have beeninvestigated as blowing agents for polyurethane based foams due to theirlow ozone depletion potentials. Some hydrofluorocarbons are used insprayable polyurethane systems to form polyurethane foams that exhibitimproved cell structure and that can be processed at a low temperatureranges. These polyurethane foams also resist excessive creep and exhibitimproved dimensional stability as compared to their counterparts.

However, to form these foams and utilize the sprayable frothpolyurethane systems, polyisocyanates and polyols must be sprayed ontosurfaces, thereby generating potentially dangerous emissions. Amounts ofemissions are typically dependent on a physical nature of a componentbeing sprayed, work practices, environmental conditions (e.g.temperature, ventilation, and air flow). Polyisocyanates are believed tocause irritation and sensitization of eyes, skin, and respiratorysystems upon contact and with repeated exposure. As a result, theOccupational Safety and Health Administration (OSHA) has set PermissibleExposure Limits (PELs) for polyisocyanates. These limits are notsupposed to be exceeded at any time in a workspace. The PEL formethylene diphenyl diisocyanate (MDI) is 0.2 mg/m³ (˜20 ppb). Inaddition, the American Conference of Governmental Industrial Hygienists(ACGIH) has established Threshold Limit Values (TLVs) for airborneconcentrations of polyisocyanates to which a worker may be consistentlyexposed for an eight hour period with no adverse health effects. TheACGIH TLV for MDI is 0.051 mg/m³ (˜5 ppb). Many methods used to measureMDI emissions are the result of industrial hygiene practices and handson experience by the industry Trade Associations (e.g. III, CPI and theDiisocyanate Panel of the ACC). Typically, a modification of the OSHAmethod 47, using impingers backed up with 13 mm filters, can be used andcan allow greater sensitivity and capture of the aerosol, both in theimpinger and filter, for subsequent analysis.

Typical sprayable froth polyurethane systems produce amounts ofpolyisocyanates in the air that exceed both the established PELs andTLVs thus requiring use of respirators, expensive engineering controls,and other protective equipment. Accordingly, there remains anopportunity to develop an improved polyurethane system.

SUMMARY OF THE DISCLOSURE AND ADVANTAGES

The instant disclosure provides a polyurethane spraying system used tominimize emissions of the polyisocyanate while spraying the mixture ontothe surface. The system includes a first reactant supply tank includingthe resin composition and a second reactant supply tank including thepolyisocyanate. The system also includes a non-gaseous pump that iscoupled with the first and second reactant supply tanks. The systemfurther includes a mixing apparatus that is coupled with the first andsecond reactant supply tanks for mixing the resin composition and thepolyisocyanate prior to spraying. Still further, the system includes aspray nozzle that is coupled with the mixing apparatus and thatminimizes emissions of the polyisocyanate while the mixture is sprayedonto the surface.

The spray nozzle includes a nozzle body having a longitudinal axis,upstream and downstream ends opposite each other, and a passage definedby said nozzle body and in fluid communication with said upstream anddownstream ends along said longitudinal axis for receiving the mixture.The spray nozzle also includes a spraying orifice defined by the nozzlebody and disposed at the downstream end of the nozzle body transverse tothe longitudinal axis for spraying the mixture at a spray anglecorresponding to a control spray angle of from 15 to 125 degreesmeasured at a pressure of from 10 to 40 psi using water as a standard.

The polyisocyanate and the resin composition of this disclosure react toform a polyurethane foam that cures faster than conventional sprayedfoams and that has a minimized ozone depleting potential, thusincreasing environmental friendliness. The spray nozzle used to spraythe mixture of the polyisocyanate and the resin composition minimizesemissions of the polyisocyanate generated by spraying the mixture andallows the mixture to be sprayed in closed and/or non-ventilatedenvironments with minimized risk of over exposure to the polyisocyanate.The spray nozzle and method of this disclosure also minimize a need touse respirators and protective equipment when spraying the mixture dueto the minimized emissions of the polyisocyanate. Furthermore, the spraynozzle also allows for effective and efficient distribution of themixture thereby reducing overspray and waste.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

Other advantages of the present disclosure will be readily appreciated,as the same becomes better understood by reference to the followingdetailed description when considered in connection with the accompanyingdrawings wherein:

FIG. 1a is a side plan view of one embodiment of the spray nozzle ofthis disclosure that produces a flat spray pattern;

FIG. 1b is a perspective view of the spray nozzle of FIG. 1 a;

FIG. 2a is a side plan view of a second embodiment of the spray nozzleof this disclosure that produces a flat spray pattern;

FIG. 2b is a perspective view of the spray nozzle of FIG. 2 a;

FIG. 3a is a side plan view of a third embodiment of the spray nozzle ofthis disclosure that produces a flat spray pattern;

FIG. 3b is a perspective view of the spray nozzle of FIG. 3 a;

FIG. 4a is a side plan view of a fourth embodiment of the spray nozzleof this disclosure that produces a flat spray pattern;

FIG. 4b is a perspective view of the spray nozzle of FIG. 4 a;

FIG. 5 is a perspective view of a fifth embodiment of the spray nozzleof this disclosure that produces a flat spray pattern;

FIG. 6a is a side plan view of one embodiment of the spray nozzle ofthis disclosure that produces a conical spray pattern;

FIG. 6b is a first perspective view of the spray nozzle of FIG. 6 a;

FIG. 6c is a second perspective view of the spray nozzle of FIG. 6 a;

FIG. 7a is a side plan view of a second embodiment of the spray nozzleof this disclosure that produces a conical spray pattern;

FIG. 7b is a first perspective view of the spray nozzle of FIG. 7 a;

FIG. 7c is a second perspective view of the spray nozzle of FIG. 7 a;

FIG. 8a is a side plan view of one embodiment of a flat fan spray nozzleof this disclosure and illustrates spray angle (α) and spray width (W)measured at a distance (D) from the spray nozzle;

FIG. 8b is a side plan view of one embodiment of a conical spray nozzleof this disclosure and illustrates spray angle (α) and spray width (W)measured at a distance (D) from the spray nozzle;

FIG. 9a is a side plan view of one embodiment of a flat fan spray nozzleof this disclosure and illustrates a flat spray pattern that issubstantially planar;

FIG. 9b is a magnified view of one embodiment of the flat spray patternthat is substantially planar and that is deflected;

FIG. 9c is a magnified view of a second embodiment of the flat spraypattern that is substantially planar and that has an even distribution;

FIG. 9d is a magnified view of a third embodiment of the flat spraypattern that is substantially planar and that is tapered;

FIG. 10a is a side plan view of one embodiment of a conical spray nozzleof this disclosure and illustrates a conical spray pattern;

FIG. 10b is a magnified view of one embodiment of the conical spraypattern that is a hollow cone;

FIG. 10c is a magnified view of one embodiment of the conical spraypattern that is a full cone;

FIG. 11 is a side plan view of a surface and a semicircle emanating fromthe surface and having a radius of three feet within which an amount ofemissions is determined using the NIOSH 5521 Impingement Method;

FIG. 12 is a schematic of one embodiment of the polyurethane sprayingsystem of this disclosure; and

FIG. 13 is a bar graph of the emission measurements set forth in Table 1of the Examples.

DETAILED DESCRIPTION OF THE DISCLOSURE

A method for minimizing emissions of a polyisocyanate while spraying amixture of the polyisocyanate and a resin composition onto a surface (S)to form a polyurethane foam thereon is described herein. The terminology“emissions” refers to an amount or concentration of the polyisocyanatepresent in air as produced from spraying the mixture. Typically, theemissions are measured after approximately 20, 19, 18, 17, 16, 15, 14,13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1, minutes of continuousspraying of the mixture. However, the measurement of the emissions neednot be limited to this time and may occur at any time after spraying. Itis also to be understood that the measurement of the emissions may occurat ground level, below grade, or at a heightened position such as whenon a scaffold or ladder. Alternatively, the emissions are measured at 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20,feet from the ground.

Spraying the mixture onto the surface (S) produces less than 50, andalternatively less then 45, 40, 35, 30, 35, 20, 15, 10, 9, 8, 7, 6, 5,4, 3, 2, or 1, parts of the polyisocyanate per one billion parts of air(ppb) within a semicircle emanating from the surface (S) according tothe NIOSH 5521 Impingement Method. The semicircle may have any radius,e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20, 25, 30, 35, 40, 45, or 50, feet. In one embodiment, the semicirclehas a radius (r) of 3 feet measured from the surface (S), as shown inFIG. 11. In another embodiment, the measurement of emissions occurswithin a semicircle emanating from the surface (S) and having a radius(r) of 15 feet measured from the surface (S). In this embodiment,spraying the mixture of the polyisocyanate and the resin compositiononto the surface (S) typically produces less than 25, more typicallyless than 15, still more typically less than 10, even more typicallyless than 5, still more typically less than 3, and most typically ofless than 1.2, parts of the polyisocyanate per one billion parts of air(ppb) according to the NIOSH 5521 Impingement Method. In still anotherembodiment, the measurement of emissions occurs within a semicircleemanating from the surface (S) and having a radius (r) of 18 inchesmeasured from the head of a technician spraying the mixtureapproximately 10 feet from the surface (S). In this embodiment, sprayingthe mixture of the polyisocyanate and the resin composition onto thesurface (S) typically produces less than 25, more typically less than15, still more typically less than 10, even more typically less than 5,still more typically less than 3, and most typically of less than 2,parts of the polyisocyanate per one billion parts of air (ppb) accordingto the NIOSH 5521 Impingement Method. In all of these embodiments, theemissions are typically measured according to the NIOSH 5521 ImpingementMethod, which is well understood in the art. It is to be understood thatemissions of other components of the resin composition or othercomponents used to form the polyurethane may also be reduced. Forexample, if a monomeric isocyanate is also utilized, the emissions ofthe monomeric isocyanate may also be reduced. The emissions of the othercomponents may be reduced in the same or different amounts as that ofthe polyisocyanate including those described above and below.

The surface (S) upon which the mixture is sprayed may be any surface butis typically a surface of a residential or commercial structure orbuilding, such as a single or multiple family home, a modular home, or abusiness, that typically has at least three walls, a floor, and a roof.Most typically, the surface (S) is a wall, floor, or ceiling of thebuilding. In one embodiment, the surface (S) is a wall of a building andthe mixture is sprayed on the wall of the building on-site, i.e., at aconstruction location. In another embodiment, the surface (S) is a wallof a building but the mixture is sprayed onto the wall before the wallis installed in the building, i.e., off-site of the constructionlocation. The surface (S) upon which the mixture is sprayed may be, butis not limited to, brick, concrete, masonry, dry-wall, sheetrock,plaster, metal, stone, wood, plastic, a polymer composite, orcombinations thereof. It is also contemplated that the surface (S) uponwhich the mixture is sprayed may be a surface of a vehicle or machinecomponent.

The method includes the steps of providing the polyisocyanate andproviding the resin composition. In other words, both the polyisocyanateand the resin composition are supplied for use in the method. Typically,the polyisocyanate and the resin composition are formulated off-site andthen delivered to an area where they are used. In one embodiment, themethod includes the step of heating the polyisocyanate and the resincomposition to a temperature of from 70° F. to 95° F. and morepreferably to a temperature of from 80° F. to 85° F. In anotherembodiment, the method includes the step of heating the polyisocyanateand the resin composition to a temperature of about 80° F. Withoutintending to be bound by any particular theory, it is believed that thistemperature promotes ease of flow of the polyisocyanate and the resincomposition in a polyurethane spraying system described in greaterdetail below.

As first introduced above, the polyisocyanate and the resin compositionreact to form a polyurethane foam on the surface (S). The polyurethanefoam may be rigid (i.e., have a ratio of compressive strength to tensilestrength of 0.5:1 or greater and an elongation of 10 percent or less)and may have a closed cell content of at least 90 percent. In analternative embodiment, the polyurethane foam has a closed cell contentof at least 95 percent. However, it is also contemplated that thepolyurethane foam may be flexible and/or may be further defined as anopen cell foam. The polyurethane foam may be used for any purposedincluding, but not limited to, insulation, sound-proofing, vibrationdampening, and combinations thereof. Most typically, the polyurethanefoam is used as insulation. In one embodiment, the polyurethane foam isused as a structural reinforcement in modular homes to reduce dry-wallcracking during transport of the modular homes to a home site. Thepolyurethane foam may stiffen surfaces such as the walls of the modularhomes to minimize sway and torque during transport.

The polyisocyanate of this disclosure may be a single isocyanate or mayinclude a mixture of isocyanates. Typically, the polyisocyanate isselected from, but is not limited to, the group of aliphaticisocyanates, cycloaliphatic isocyanates, araliphatic isocyanates,aromatic multivalent isocyanates, and combinations thereof. Particularlysuitable non-limiting examples of the polyisocyanate include alkylenediisocyanates having 4 to 12 carbons in an alkylene radical such as1,12-dodecane diisocyanate, 2-ethyl-1,4-tetramethylene diisocyanate,2-methyl-1,5-pentamethylene diisocyanate, 1,4-tetramethylenediisocyanate and 1,6-hexamethylene diisocyanate, cycloaliphaticdiisocyanates such as 1,3- and 1,4-cyclohexane diisocyanate,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophoronediisocyanate), 2,4- and 2,6-hexahydrotoluene diisocyanate,2,4′-dicyclohexylmethane diisocyanate, mixtures of 4,4′- and2,4′-diphenylmethane diisocyanates and polyphenylenepolymethylenepolyisocyanates (polymeric MDI), m-phenylene diisocyanate, 2,4-toluenediisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate,tetramethylene diisocyanate, cyclohexane-1,4-diisocyanate,hexahydrotoluene diisocyanate, naphthalene-1,5-diisocyanate,1-methoxyphenyl-2,4-diisocyanate, 4,4′-diphenylmethane diisocyanate,4,4′-biphenylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenyldiisocyanate, 3,3′-dimethyl-4,4′-biphenyl diisocyanate and3,3′-dimethyldiphenylmethant-4,4′-diisocyanate, 4,4′,4″-triphenylmethanetriisocyanate, toluene 2,4,6-triisocyanate;4,4′-dimethyldiphenylmethane-2,2′,5,5′-tetraisocyanate, polymethylenepolyphenylene polyisocyanate, isomers thereof, and combinations thereof.In one embodiment, the polyisocyanate is further defined as methylenediphenyl diisocyanate (MDI).

In an alternative embodiment, the polyisocyanate is further defined as amodified multivalent isocyanate. As is known in the art, modifiedmultivalent isocyanates are typically formed through partial chemicalreactions of organic diisocyanates and/or polyisocyanates. Particularlysuitable non-limiting examples of modified multivalent isocyanatesinclude diisocyanates and/or polyisocyanates having ester groups, ureagroups, biuret groups, allophanate groups, carbodiimide groups,isocyanurate groups, and/or urethane groups. The polyisocyanate mayinclude, but is not limited to, one or more urethane groups andtypically has an NCO content of from 15 to 33.6 or from 21 to 32, weightpercent, based on a total weight of the polyisocyanate. Of course, it isto be understood that the polyisocyanate is not limited to such an NCOcontent. The urethane groups of the polyisocyanate may be formed throughreaction of a base polyisocyanate, as described above, with lowmolecular weight diols, triols, dialkylene glycols, trialkylene glycols,polyoxyalkylene glycols with a number average molecular weight of up to1500 g/mol, diethylene glycol, dipropylene glycol, polyoxyethyleneglycol, polyoxypropylene glycol, polyoxyethylene glycol,polyoxypropylene glycol, and/or polyoxypropylene polyoxyethylene glycolsor -triols, and combinations thereof. The polyisocyanate may alsoinclude one or more prepolymers including isocyanate groups thattypically have an NCO content of 9 to 25 and more typically of from 14to 21, weight percent based on a total weight of the prepolymer.Alternatively, the polyisocyanate may be further defined as a liquidpolyisocyanate including one or more carbodiimide groups having an NCOcontent of from 15 to 33.6 or from 21 to 32, weight percent based on atotal weight of the polyisocyanate. Crude polyisocyanates may also beused in the compositions of the present disclosure, such as crudetoluene diisocyanate obtained by the phosgenation of a mixture oftoluenediamines or crude diphenylmethane isocyanate obtained by thephosgenation of crude isocyanates as disclosed in U.S. Pat. No.3,215,652, the disclosure of which is directed at phosgenation isexpressly incorporated herein by reference. In one embodiment, thepolyisocyanate may be any of those described in U.S. Pat. No. 6,534,556,which is hereby expressly incorporated by reference relative to thepolyisocyanates.

Referring now to the resin composition, the resin composition has ahydroxyl content of at least 400 mg KOH/g. In one embodiment, the resincomposition has a hydroxyl content of from 400 to 550 mg KOH/g. Theresin composition also typically has a viscosity of less than 500centipoises, and more typically of from 400 to 500 centipoises, measuredat 25° C. using a Brookfield Viscometer. Alternatively, the resincomposition may be as described in U.S. Pat. No. 6,534,556, which ishereby expressly incorporated by reference relative to the resincomposition.

The resin composition includes a (i) blowing agent that is a liquidunder a pressure greater than atmospheric pressure. In one embodiment,the (i) blowing agent is selected from the group consisting of volatilenon-halogenated C₂ to C₇ hydrocarbons, hydrofluorocarbons, and mixturesthereof. In another embodiment, the (i) blowing agent is a physicallyactive blowing agent, such as a C₁-C₄ hydrofluorocarbon having a boilingpoint of 26° C. or less. As is known in the art, physically activeblowing agents typically boil at an exotherm foaming temperature orless, most typically at 50° C. or less. Examples of particularlysuitable physically active blowing agents include, but are not limitedto, volatile non-halogenated hydrocarbons having two to seven carbonatoms such as alkanes, alkenes, cycloalkanes having up to 6 carbonatoms, dialkyl ether, cycloalkylene ethers and ketones, andhydrofluorocarbons (HFCs).

The (i) blowing agent may have a zero ozone depletion potential. Inother embodiments, the (i) blowing agent has an ozone depletionpotential of less than 1.1, less than 1, less than 0.8, less than 0.6,less than 0.1, or from 0.01 to 0.1. As is known in the art, theterminology “ozone depletion potential” is defined as a ratio of animpact on ozone of a first chemical compared to an impact on ozone of asimilar mass of trichlorofluoromethane (R-11/CFC-11). In other words,ozone depletion potential is a ratio of global loss of ozone due to agiven chemical to a global loss of ozone due to CFC-11 of the same mass.

In still other embodiments, the (i) blowing agent is further defined as,but is not limited to, a volatile non-halogenated hydrocarbon such as alinear or a branched alkane such as butane, isobutane,2,3-dimethylbutane, n- and isopentanes, n- and isohexanes, n- andisoheptanes, n- and isooctanes, n- and isononanes, n- and isodecanes, n-and isoundecanes, and n- and isodedecanes, alkenes such as 1-pentene,2-methylbutene, 3-methylbutene, and 1-hexene, cycloalkanes such ascyclobutane, cyclopentane, and cyclohexane, linear and/or cyclic etherssuch as dimethyl ether, diethyl ether, methyl ethyl ether, vinyl methylether, vinyl ethyl ether, divinyl ether, tetrahydrofuran and furan,ketones such as acetone, methyl ethyl ketone and cyclopentanone, isomersthereof, and combinations thereof.

In another embodiment, the (i) blowing agent is further defined as ahydrofluorocarbon such as difluoromethane (HFC-32),1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane(HFC-134), 1,1-difluoroethane (HFC-152a), 1,2-difluoroethane (HFC-142),trifluoromethane, heptafluoropropane (R-227a), hexafluoropropane(R-136), 1,1,1-trifluoroethane, 1,1,2-trifluoroethane, fluoroethane(R-161), 1,1,1,2,2-pentafluoropropane, pentafluoropropylene (R-2125a),1,1,1,3-tetrafluoropropane, tetrafluoropropylene (R-2134a),difluoropropylene (R-2152b), 1,1,2,3,3-pentafluoropropane,1,1,1,3,3-pentafluoro-n-butane, and 1,1,1,3,3-pentafluoropentane(245fa), isomers thereof, and combinations thereof. In an alternativeembodiment, the (i) blowing agent is further defined as1,1,1,2-tetrafluoroethane (HFC-134a), also known as R-134a. HFC-134a hasa boiling point of 247 K (−26° C. at 760 mm/Hg) and readily vaporizes atatmospheric pressure. Alternatively, the (i) blowing agent may be asdescribed in U.S. Pat. No. 6,534,556, which is hereby expresslyincorporated by reference relative to the blowing agents. Typically, the(i) blowing agent is present in an amount of from 2 to 20, moretypically in an amount of from 5 to 15, and most typically in an amountof from 7 to 10 parts by weight per 100 parts by weight of the resincomposition. However, the amount of the (i) blowing agent used typicallydepends on a desired density of the polyurethane foam and solubility ofthe (i) blowing agent in the resin composition. It is desirable tominimize amounts of the (i) blowing agent used to reduce costs.

In addition to the (i) blowing agent, the resin composition alsoincludes a (ii) first polyol. The first polyol is selected from thegroup of a Mannich polyol, an autocatalytic polyol, and combinationsthereof. As is known in the art, autocatalytic polyols typically includeone or more tertiary nitrogen groups (e.g. amine groups) and typicallyrequire less capping with primary hydroxyl groups to achieve suitableperformance. Suitable non-limiting examples of the autocatalytic polyolinclude Pluracol® SG 360, Pluracol® P824, Pluracol® P736, Pluracol®P922, Pluracol® P1016, and combinations thereof. Each of theseautocatalytic polyols are commercially available from BASF Corporation.Of course, the autocatalytic polyol is not limited to those describedabove and may be any known in the art. In one embodiment, theautocatalytic polyol is as defined in U.S. Pat. No. 6,924,321, which isexpressly incorporated herein by reference relative to this embodiment.In one embodiment, no other catalyst is used in conjunction with theautocatalytic polyol. However, one or more catalysts may be used asselected by one of skill in the art.

The Mannich polyol may be any known in the art but typically has aviscosity of at least 4,000 centipoise at 25° C. The Mannich polyol istypically formed by alkoxylating a Mannich compound (e.g. a condensationproduct of phenol or a substituted phenol (e.g. nonylphenol),formaldehyde, and an alkanolamine, such as diethanolamine). As is knownin the art, this alkoxylation may include premixing the phenol with thediethanolamine and then adding formaldehyde at a temperature below atemperature of Novolac formation. Typically, after the formaldehydereacts, water is stripped to provide a crude Mannich reaction product.The Mannich reaction product then may be alkoxylated with an alkyleneoxide such as propylene oxide, ethylene oxide, or combinations thereof.The alkylene oxide typically includes from 80 wt. % to about 100 wt. %propylene oxide and less than about 20 wt. % ethylene oxide.Alkoxylation of Mannich reaction products is described in U.S. Pat. Nos.3,297,597 and 4,137,265, the disclosures of which are herein expresslyincorporated by reference. In one embodiment, the Mannich polyol is asdefined in U.S. Pat. No. 6,495,722, which is expressly incorporatedherein by reference relative to this embodiment. Typically, Mannichpolyols have at least one nitrogen containing moiety (e.g.—N(CH₂)₄(OH)₂) singly bonded to a CH₂ moiety.

More specifically, alkoxylation of the Mannich reaction product istypically carried out by introducing the propylene oxide to the Mannichreaction product under pressure. No added catalyst is typically neededsince basic nitrogen atoms in the reaction product provide sufficientcatalytic alkoxylation. Typically, alkoxylation proceeds at temperaturesof from 30° C. to 200° C. and more typically at temperatures of from 90°C. to 120° C. At these temperatures, phenolic hydroxyl groups andalkanolamino hydroxyl groups react to form hydroxypropyl groups. Anyunreacted or partially reacted compounds are typically removed from the(ii) first polyol. In one embodiment, the Mannich polyol is as describedin U.S. Pat. No. 6,534,556, which is hereby expressly incorporated byreference relative to the Mannich polyols. In another embodiment, theMannich polyol includes an aromatic, amino polyol having an aminocontent of at least 2.8 meq/g. Typically, the Mannich polyol is presentin an amount of from 10 to 60, more typically in an amount of from 20 to50, and most typically in an amount of from 20 to 40 parts by weight per100 parts by weight of the resin composition.

In addition, the resin composition includes (iii) at least oneadditional polyol other than the (ii) first polyol. The (iii) additionalpolyol may be any known in the art and has at least twoisocyanate-reactive hydrogen atoms. The (iii) additional polyoltypically has an average hydroxyl number of from 150 to 800 mg KOH/g,but is not limited to such a value. Suitable non-limiting examples ofthe (iii) additional polyol include polythioether polyols, polyesteramides and polyacetals containing hydroxyl groups, aliphaticpolycarbonates including hydroxyl groups, amine-terminatedpolyoxyalkylene polyethers, polyester polyols, polyoxyalkylene polyetherpolyols, and combinations thereof.

The polyester polyols may include up to about 40 weight percent freeglycol and may be further defined as ε-caprolactone or as ahydroxycarboxylic acids, e.g. ω-hydroxycaproic acid. The polyesterpolyol may be formed from organic dicarboxylic acids having 2 to 12carbon atoms, aliphatic dicarboxylic acids having 4 to 6 carbon atoms,or multivalent alcohols, such as diols, having 2 to 12 carbon atoms andmost preferably 2 to 6 carbon atoms. Suitable non-limiting examples ofdicarboxylic acids include succinic acid, glutaric acid, adipic acid,suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid,maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalicacid, and combinations thereof. Alternatively, dicarboxylic acidderivatives may also be used and may include, for example, dicarboxylicacid mono- or di-esters of alcohols having 1 to 4 carbon atoms, ordicarboxylic acid anhydrides. Dicarboxylic acid mixtures of succinicacid, glutaric acid and adipic acid in weight ratios of20-35:35-50:20-32 parts by weight are preferred. Typical examples ofdivalent and multivalent alcohols that may be used to form the polyesterpolyol include ethanediol, diethylene glycol, 1,2- and 1,3-propanediol,dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,1,10-decanediol, glycerine and trimethylolpropanes, tripropylene glycol,tetraethylene glycol, tetrapropylene glycol, tetramethylene glycol,1,4-cyclohexane-dimethanol, ethanediol, diethylene glycol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and combinationsthereof.

The polyester polyol can be formed by polycondensation/esterification oforganic polycarboxylic acids, e.g. aromatic or aliphatic polycarboxylicacids and/or derivatives thereof, and multivalent alcohols in theabsence of catalysts or in an inert atmosphere such as nitrogen, carbondioxide, or a noble gas. Typically, the polyester polyol is formed attemperatures of from 150° C. to 250° C. and more typically attemperatures of from 180° C. to 220° C. The reaction can be carried outas a batch process or as a continuous process and may include a catalystincluding iron, cadmium, cobalt, lead, zinc, antimony, magnesium,titanium and/or tin. To produce the polyester polyols, the organicpolycarboxylic acids and multivalent alcohols are preferably condensedin a mole ratio of 1:1-1.8 and more preferably in a mole ratio of1:1.05-1.2.

Alternatively, aromatic polyester polyols can be formed using esterby-products from the manufacture of dimethyl terephthalate, polyalkyleneterephthalates, phthalic anhydride, residues from the manufacture ofphthalic acid or phthalic anhydride, terephthalic acid, residues fromthe manufacture of terephthalic acid, isophthalic acid, trimelliticanhydride, and combinations thereof.

Polyether polyols can be formed by anionic polymerization with alkalihydroxides such as sodium hydroxide or potassium hydroxide or alkalialcoholates, such as sodium methylate, sodium ethylate, or potassiumethylate or potassium isopropylate as catalysts and with the addition ofat least one initiator molecule preferably including from 2 to 8 andmore preferably from 3 to 8, reactive hydrogen atoms. Alternatively,cationic polymerization with Lewis acids such as antimony pentachlorideand boron trifluoride etherate can be used. The polyether polyols may beprepared from any initiators known in the art including, but not limitedto, ethylene glycol, propylene glycol, dipropylene glycol, trimethyleneglycol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol,1,7-heptanediol, hydroquinone, resorcinol glycerol, glycerine,1,1,1-trimethylol-propane, 1,1,1-trimethylolethane, pentaerythritol,1,2,6-hexanetriol, a-methyl glucoside, sucrose, sorbitol,2,2-bis(4-hydroxyphenyl)-propane, tetrahydrofuran and alkyleneoxide-tetrahydrofuran mixtures, epihalohydrins such as epichlorohydrin,and combinations thereof. These initiators can react with any suitablealkylene oxide such as 1,3-propylene oxide, 1,2- and 2,3-butylene oxide,amylene oxides, styrene oxide, ethylene oxide, 1,2-propylene oxide, andcombinations thereof.

Suitable non-limiting examples of polyether polyols that may be includedin the resin composition include polyoxyethylene glycol,polyoxypropylene glycol, polyoxybutylene glycol, polytetramethyleneglycol, block copolymers, polyoxypropylene glycol, polyoxyethyleneglycol, poly-1,2-oxybutylene glycol, polyoxyethylene glycol,poly-1,4-tetramethylene glycol, polyoxyethylene glycol, copolymerglycols prepared from blends or sequential addition of two or morealkylene oxides, and combinations thereof. Particularly preferredpolyether polyols include, but are not limited to, Voranol® 370 polyol,a sucrose based polyether polyol having a hydroxyl number ofapproximately 370 and commercially available from Dow Chemical,Pluracol® 450 and 550 polyether tetrols having hydroxyl numbers ofapproximately 560 and 450, respectively and commercially available fromBASF Corporation, LHT-240 a polyether triol having a hydroxyl number ofapproximately 270 and commercially available from AC West VirginiaPolyol Company.

In one embodiment, the (iii) additional polyol is formed fromcondensation of an amine initiator and an alkylene oxide. Suitable amineinitiators include, but are not limited to, aniline,N-alkylphenylenediamines, 2,4′-2,2′, and 4,4′-methylenedianiline, 2,6-or 2,4-toluenediamine, vicinal toluenediamines, o-chloro-aniline,p-aminoaniline, 1,5-diaminonaphthalene, methylene dianiline,condensation products of aniline and formaldehyde, isomericdiaminotoluenes, aliphatic amines such as mono-, di-, andtrialkanolamines, ethylene diamine, propylene diamine,diethylenetriamine, methylamine, ethanolamine, diethanolamine, N-methyl-and N-ethylethanolamine, N-methyl- and N-ethyldiethanolamine,triethanolamine, triisopropanolamine, 1,3-diaminopropane,1,3-diaminobutane, 1,4-diaminobutane, and combinations thereof.Alternatively, the (iii) additional polyol may be formed fromcondensation of a thiol initiator and an alkylene oxide. The thiolinitiator may include, but is not limited to, a condensation product ofthiodiglycol, a reaction product of a dicarboxylic acid and a thioetherglycol, alkanethiols including at least two —SH groups such as1,2-ethanedithiol, 1,2-propanedithiol, 1,2-propanedithiol, and1,6-hexanedithiol, alkene thiols such as 2-butene-1,4-dithiol, alkynethiols such as 3-hexyne-1,6-dithiol, and combinations thereof.Alternatively, the (iii) additional polyol may include polyester amidefunctionality. In one embodiment, a polyacetal is condensed with analkylene oxide. Still further, the (iii) additional polyol may be any ofthe additional polyols described in U.S. Pat. No. 6,534,556, which isexpressly incorporated herein by reference relative to these additionalpolyols. It is also to be understood that the (iii) additional polyolmay be further defined as a single polyol or as two or more polyols thatare combined together. In other words, more than one additional polyolmay be included in the resin composition. In various embodiments, two,three, four, and five additional polyols are included in the resincomposition.

The (iii) additional polyol is typically present in an amount of from 10to 60, more typically in an amount of from 20 to 50, and most typicallyin an amount of from 20 to 40 parts by weight per 100 parts by weight ofthe resin composition. In one embodiment, the (iii) additional polyol isfurther defined as a sucrose-initiated polyether polyol that present inan amount of less than or equal to about 20 weight percent based on atotal weight of the resin composition. In another embodiment, the (iii)additional polyol is further defined as a polyether tetrol that ispresent in an amount of less than or equal to about 20 weight percentbased on a total weight of the resin composition. In a furtherembodiment, the (iii) additional polyol is further defined as apolyether triol that is present in an amount of less than or equal toabout 30 weight percent based on a total weight of the resincomposition.

The resin composition may also optionally include (iv) a catalyst. The(iv) catalyst may include one or more catalysts and typically includes acombination of catalysts. In one embodiment, the (iv) catalyst includesa polyurethane curing catalyst. Typically, the polyurethane curingcatalysts accelerate a reaction of the polyisocyanate and the firstpolyol and/or the (iii) additional polyol. The polyurethane curingcatalysts may also shorten tack time, promote green strength andminimize foam shrinkage. Suitable polyurethane curing catalysts include,but are not limited to, organometallic catalysts, such as organo-leadcatalysts, tin, titanium, copper, mercury, cobalt, nickel, iron,vanadium, antimony and manganese catalysts, and combinations thereof.The polyurethane curing catalyst may be further defined as a mixture oflead octoate and lead naphthanate. In one embodiment, the (iv) catalystis substantially free of lead and typically includes less than 0.1, moretypically of less than 0.01, and most typically of less than 0.001 partsby weight of lead per 100 parts by weight of the (iv) catalyst. Inanother embodiment, the (iv) catalyst is free of lead. In oneembodiment, the (iv) catalyst includes lead octanoate that present in anamount of from 0.3 to 0.9 weight percent based on a total weight of theresin composition. In a further embodiment, the (iv) catalyst is asdescribed in U.S. Pat. No. 6,534,556, which is hereby expresslyincorporated by reference relative to these catalysts.

Suitable polyurethane curing catalysts include, but are not limited to,tertiary amines such as triethylamine,3-methoxypropyldimethylamine,triethylenediamine, tributylamine, dimethylcyclohexylamine,dimethylbenzylamine, N-methyl-, N-ethyl- and N-cyclohexylmorpholine,N,N,N′,N′-tetramethylethylenediamine, N,N,N′,N′-tetramethylbutanediamineor -hexanediamine, N,N,N′-trimethyl isopropyl propylenediamine,pentamethyldiethylenetriamine, tetramethyldiaminoethylether,bis(-dimethylaminopropyl)urea, dimethylpiperazine,1-methyl-4-dimethylaminoethylpiperazine, 1,2-dimethylimidazole,1-azabicylo[3.3.0]octane and preferably 1,4-diazabicylo[2.2.2]octane,and alkanolamine compounds, such as triethanolamine,triisopropanolamine, N-methyl- and N-ethyldiethanolaminedimethylethanolamine, and combinations thereof.

Apart from polyurethane curing catalysts, the (iv) catalyst may alsoinclude a blowing catalyst that promotes a reaction of the (i) blowingagent. The blowing catalyst may include tertiary amine ethers such asN,N,N,N″-tetramethyl-2,2′-diaminodiethyl ether,2-dimethylaminoethyl-1,3-dimethylamineopropyl ether,N,N-dimorpholinoethyl ether, and combinations thereof. The blowingcatalyst can be used neat or dissolved in a carrier such as a glycol. Invarious embodiments, the blowing catalyst is further defined aspentamethyldiethylenetriamine and/or polyoxypropylenediamine and ispresent in an amount of from 0.01 to 3.0 weight percent based on a totalweight of the resin composition.

The (iv) catalyst may further include a gelation catalyst that promotesgelling of the resin composition as opposed to foaming. The gelationcatalyst typically includes an amine catalyst such as triethylenediaminein a dipropylene glycol carrier. This type of catalyst is commerciallyavailable from Air Products Corp. under the trade name DABCO® LV-33. Inone embodiment, the gelation catalyst is present in an amount of from0.01 to 3.0 weight percent based on a total weight of the resincomposition.

In addition to the (iv) catalyst, the resin composition may alsooptionally include a (v) surfactant. The (v) surfactant typicallysupports homogenization of the (i) blowing agent, (ii) first polyol and(iii) additional polyol and regulates a cell structure of thepolyurethane foam. Non-limiting examples of suitable (v) surfactantsinclude salts of sulfonic acids, e.g. alkali metal and/or ammonium saltsof oleic acid, stearic acid, dodecylbenzene- ordinaphthylmethane-disulfonic acid, and ricinoleic acid, foam stabilizerssuch as siloxaneoxyalkylene copolymers and other organopolysiloxanes,oxyethylated alkyl-phenols, oxyethylated fatty alcohols, paraffin oils,castor oil esters, ricinoleic acid esters, Turkey red oil and groundnutoil, and cell regulators, such as paraffins, fatty alcohols, anddimethylpolysiloxanes. In one embodiment, the (v) surfactant is anon-silicone surfactant. In other words, in this embodiment, the (v)surfactant is free of silicone. A particularly suitable non-siliconesurfactant is LK-443 commercially available from Air ProductsCorporation. The (v) surfactant may be included in the resin compositionin an amount of from 0.001 to 5 weight percent. However, these amountsare not intended to limit this disclosure.

The resin composition may also optionally include (vi) water. The watermay be of any purity including tap, well, de-ionized, distilled, and thelike. Typically, the water is present in a minimized amount. Forexample, in various embodiments where water is used, the water ispresent in amounts of from 0.1 to 10, more typically of from 0.1 to 5,and most typically of from 1 to 3, parts by weight of water per 100parts by weight of the composition. The water may be included asdescribed in U.S. Pat. No. 6,534,556, which is hereby expresslyincorporated by reference relative to the water. In one embodiment, thewater is used as a blowing agent.

Further, the resin composition may optionally include an (vii) additiveor a plurality of additives. The additive may be selected from the groupof chain extenders, anti-foaming agents, processing additives, chainterminators, solvents, surface-active agents, adhesion promoters, flameretardants, anti-oxidants, dyes, ultraviolet light stabilizers, fillers,thixotropic agents, stabilizers, fungicides, pigments, dyes,bacteriostats, and combinations thereof. In various embodiments, the(vi) additive is a flame retardant or a mixture of flame retardants.Examples of suitable flame retardants include, but are not limited to,tricresyl phosphate, tris(2-chloroethyl)phosphate,tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate, redphosphorus, aluminum oxide hydrate, antimony trioxide, arsenic oxide,ammonium polyphosphate (Exolit®) and calcium sulfate, molybdenumtrioxide, ammonium molybdate, ammonium phosphate,pentabromodiphenyloxide, 2,3-dibromopropanol, hexabromocyclododecane,dibromoethyldibromocyclohexane, expandable graphite or cyanuric acidderivatives, melamine, corn starch, and combinations thereof. The resincomposition typically includes from 2 to 40, and more typically from 5to 20, parts by weight of the additive per 100 parts by weight of theresin composition. The additive may be as described in U.S. Pat. No.6,534,556, which is hereby expressly incorporated by reference relativeto the additive.

In one embodiment, the chemistry of the reaction between an isocyanate(typically MDI) and a resin (comprising a polyol, e.g. 50 to 60 wt % forclosed cell foams or 30 to 50 wt % for open cell foams) influences oneor more parameters of the system and/or method of this disclosure. Forexample, to form a closed cell foam, a blowing agent is typically usedto obtain a desired density that may be from about 1.9 to about 2.5pound per cubic feet. The blowing agent may volatilize into a gas due tothe heat of the reaction. For some closed cell foams, the dominantreaction is typically between the isocyanate and polyol. There may alsobe another reaction between water molecules and isocyanate. To form anopen cell foam, the reactions tend to be more balanced. A reactionbetween water and an isocyanate may be more prevalent in the formationof open cell foams than in closed cell foams. These reactions may occurat a one to one by volume ratio between the isocyanate and the polyol.In one embodiment, a typical resin used to form closed cell foamsincludes one or more polyester polyols and one or more polyetherpolyols.

In various embodiments, one or more of the following components may beutilized to form, for example, open and/or closed cell foams forinsulation, roofing, etc:

Approximate Weight Component Non-Limiting Examples of the ComponentPercentages Polyester Polyethylene terephthalate, diethylene glycol(DEG), phthalic 35-45 polyol acid, and/or terephthalic acid PolyetherPhenol or nonylphenol, formaldehyde, and/or amines, one or 10-25 polyolmore with propylene oxide and optionally ethylene oxide PolyetherSucrose, glycerin, propylene glycol, and/or propylene oxide  8-10 polyolFire retardant Tetrabromo phthalic anhydride diol  5-10 Fire retardanttris-(chloroisopropyl) phosphate and/or triethylphosphate  5-10Catalysts Combinations of tertiary amines of varying chemical structure:3-7 dimethylethanolamine (DMEA); triethylenediamine (TEDA);pentamethyldiethylenetriamine; and/or2-{{2-(Dimethylamino)ethyl}methylamino}-ethanol Catalysts Bismuthcarboxylic acids, e.g. Bi-octoate, Bi-neodecanoate, 1-2 and/orBi-ethylhexanoate be diluted with mineral spirits or straight acid,and/or potassium salts Surfactant DABCO DC193  1 Blowing agent1,1,1,1,1-pentafluoropropane  8-10 Blowing agent Water 1.7-1.9 Total 100Polyether High molecular weight, primary hydroxyl terminated triol with10-25 polyol typical functionality of about 3 Polyether Sucrose,glycerin, propylene glycol, and/or propylene oxide 10-25 polyolCrosslinker Glycerin and/or diethylene glycol (DEG) 0-3 Fire retardantTetrabromo phthalic anhydride diol  5-10 Fire retardanttris-(chloroisopropyl) phosphate and/or triethylphosphate  5-20Catalysts Combinations of tertiary amines of varying chemical structure:3-7 dimethylethanolamine (DMEA); triethylenediamine (TEDA);pentamethyldiethylenetriamine; and/or2-{{2-(Dimethylamino)ethyl}methylamino}-ethanol Surfactant DABCO DC1931-4 Blowing agent Water 12-30 Total 100 Polyester Polyethyleneterephthalate, diethylene glycol (DEG), phthalic polyol acid and/orterephthalic acid Polyether Phenol or nonylphenol, formaldehyde, and/oramines, one or polyol more with propylene oxide and optionally ethyleneoxide Polyether Sucrose, glycerine, propylene glycol, and/or propyleneoxide polyol Crosslinker Glycerin and/or diethylene glycol (DEG) Fireretardant Tetrabromo phthalic anhydride diol Fire retardanttris-(chloroisopropyl) phosphate and/or triethylphosphate CatalystsCombinations of tertiary amines of varying chemical structure:dimethylethanolamine (DMEA); triethylenediamine (TEDA);pentamethyldiethylenetriamine; and/or2-{{2-(Dimethylamino)ethyl}methylamino}-ethanol Catalysts Bismuthcarboxylic acids, e.g. Bi-octoate, Bi-neodecanoate, and/orBi-ethylhexanoate be diluted with mineral spirits or straight acid,and/or potassium salts Surfactant DABCO DC193 Surfactant DABCO LK443Blowing agent 1,1,1,1,1-pentafluoropropane Blowing agent Water

Referring back to the method, the method also includes the step ofcombining the resin composition with the polyisocyanate in the absenceof other blowing agents to form the mixture. Typically, uponcombination, the mixture is further defined as a “froth foaming mixture”because the (i) blowing agent spontaneously vaporizes when exposed toatmospheric pressure the polyisocyanate and the resin composition arecombined and processed. In other words, the (i) blowing agent acts as afrothing agent to foam the mixture on a surface of a substrate uponwhich the mixture is applied.

The polyisocyanate and the resin composition may be combined by anymeans known in the art to form the mixture, e.g. in a proportioner.Typically, the step of combining occurs in a mixing apparatus such as astatic mixer, impingement mixing chamber, or a mixing pump. In oneembodiment, the step of mixing occurs in a static mixing tube.Alternatively, the polyisocyanate and the resin composition may becombined in a spray nozzle (20), so long as the mixture is sprayedaccording to this disclosure. The polyisocyanate and the resincomposition are typically combined at an isocyanate index of from about100 to 140, more typically from 100 to 130, even more typically from 110to 120, and most typically from 110 to 115.

In one embodiment, the polyisocyanate and the resin composition arecombined to form the mixture in the absence of blowing agents that arenot the (i) blowing agent described above. In still another embodiment,the (i) blowing agent is added to the resin composition as the resincomposition is combined with the polyisocyanate.

In another embodiment, the polyisocyanate and the resin composition arecombined with a stream of air typically having a pressure of from 1 to5, more typically of from 2 to 4, and most typically of about 3, psi. Inthis embodiment, the air is not functioning as a blowing agent and isinstead functioning as a mixing agent. It is contemplated that thepolyisocyanate may be combined with the stream of air before beingcombined with the resin composition. Alternatively, the resincomposition may be combined with the stream of air before being combinedwith the polyisocyanate. Further, the polyisocyanate and the resincomposition may be combined simultaneously with the stream of air. Thestream of air is thought to aid in mixing and promote even spraying anddistribution of the mixture, as described in greater detail below.

The method also includes the step of spraying the mixture onto thesurface (S) to form the polyurethane foam thereon. Typically, themixture is sprayed at a spray rate of from 1 to 30, from 5 to 25, from 5to 20, from 5 to 10, from 5 to 15, from 15 to 20, from 20 to 25, from 25to 30, from 6 to 17, or about 15, lbs/min. Also, the mixture istypically sprayed at a pressure of less than 250 psi and most typicallyat a pressure of from 230 to 240 psi. It is contemplated that themixture may be sprayed at any rate or range of rates within the rangesset forth above. Similarly, it is contemplated that the mixture may besprayed at any pressure or range of pressures within the ranges setforth above.

In the method, the mixture is sprayed with minimized emissions from thespray nozzle (20). The spray nozzle (20) through which the mixture issprayed is typically a flat fan nozzle or a cone nozzle. The terminology“flat ‘fan’” and “cone” are well known to those in the art of nozzledesign. Useful spray nozzles (20) are commercially available fromSpraying Systems Co. of Wheaton, Ill. under the trade names VeeJet®,WashJet®, FloodJet®, FlatJet®, FullJet®, and FoamJet®. Particularlyuseful spray nozzles (20) include the VeeJet® flat fan nozzles andWashJet® cone nozzles. FIGS. 1-5 illustrate particularly useful flat fannozzles while FIGS. 6 and 7 illustrate particularly useful cone nozzles.Of course, the instant disclosure is not limited to use of theseparticular spray nozzles (20) and may utilize any flat fan or conenozzles known in the art or any other type of nozzle so long as themixture is sprayed according to this disclosure. The spray nozzle (20)may be formed from any material known in the art but is typically formedfrom brass, stainless steel, Kynar®, hardened stainless steel, and/orceramic.

The mixture is sprayed through the spray nozzle (20) at a spray angle(α) that corresponds to a control spray angle of from 15 to 125 degreesmeasured at a pressure of from 10 to 40 psi using water as a standard,as illustrated in FIGS. 8 and 9. Said differently, the actual sprayangles measured when spraying the instant mixture through the spraynozzle (20) may be different from the control spray angle rangesdescribed herein due to the viscosity of the mixture as compared to theviscosity of the water standard. As just one example, the viscosity ofthe mixture may be greater than the viscosity of the water standard. Assuch, the actual spray angle that is emitted from the spray nozzle (20)when spraying the mixture may be different from the spray angle thatwould otherwise be produced if water was sprayed through the same spraynozzle (20). Accordingly, the control spray angle refers to a sprayangle that is achieved when spraying water through the spray nozzle (20)at a pressure of from 10 to 40 psi.

In one embodiment, the spray angle (α) is further defined ascorresponding to a control spray angle of from 15 to 120 degrees whenmeasured at a pressure of 40 psi using water as a standard. In thisembodiment, the flat spray pattern typically has a spray width (W) thatcorresponds to a control spray width of from 2 to 30 inches measured ata distance (D) of about 10 inches from the spray nozzle (20), as shownin FIG. 8a , also using water as a standard. Said differently, theactual spray widths measured when spraying the instant mixture throughthe spray nozzle (20) may be different from the control spray widthdescribed herein due to the viscosity of the mixture as compared to theviscosity of the water standard. Just as above, the viscosity of themixture may be greater than the viscosity of the water standard. Assuch, the actual spray width that is emitted from the spray nozzle (20)when spraying the mixture may be different from the spray width thatwould otherwise be produced if water was sprayed through the same spraynozzle (20). Accordingly, the control spray width refers to a spraywidth that is achieved when spraying water through the spray nozzle (20)measured at a distance (D) of about 10 inches from the spray nozzle(20).

The mixture may be sprayed in a flat spray pattern that is substantiallyplanar. It is to be understood that the terminology “substantiallyplanar” refers to a spray pattern that is planar, nearly planar and/orexhibiting characteristics associated with a planar element, withoutnecessarily being restricted to this meaning. Typically, spray nozzles(20) distribute the mixture as a flat fan or sheet-type of spray. As isknown in the art of nozzle design, there are several different types offlat spray nozzles (20) including axial and deflector configurations.Typically, narrower spray angles produce streams of the mixture athigher pressures at the surface (S). In one embodiment, the flat spraypattern has a tapered pattern, as is known and defined in the art. Inanother embodiment, the flat spray pattern has an even distribution, asis also known and defined in the art. Typically, the flat spray patternthat is substantially planar is of the type that is sprayed through aflat spray nozzle.

In other similar embodiments, the spray angle (α) corresponds to acontrol spray angle of 15, 25, 40, 50, 65, 80, 95, 110, or 120 degreeswhen measured at a pressure of 40 psi using water as a standard. Theterminology “flat spray pattern” is well recognized to those of skill inthe art and is approximately illustrated in FIG. 9a . It is contemplatedthat the mixture may be sprayed at any spray angle or within any rangeof spray angles within the ranges set forth above.

Alternatively, the spray angle (α) may be further defined ascorresponding to a control spray angle of from equivalent to 15 to 125degrees when measured at a pressure of 10 psi in a conical spray patternusing water as a standard. In one embodiment, the mixture is sprayed ina conical spray pattern that has a spray width (W) that corresponds to acontrol spray width of from 2 to 30 inches measured at a distance (D) ofabout 10 inches from the spray nozzle (20), as shown in FIG. 8b , alsousing water as a standard. In other embodiments, the spray angle (α) isfurther defined as corresponding to a control spray angle of from 50 to80 degrees when measured at a pressure of 10 psi using water as astandard or corresponding to a control spray angle of from 120 to 125degrees when measured at a pressure of 10 psi using water as a standard,as shown in FIG. 9b . In other similar embodiments, the spray angle (α)is further defined as corresponding to a control spray angle of about 60or 70 degrees when measured at a pressure of 10 psi using water as astandard. The terminology “conical spray pattern” is known to those ofskill in the art of nozzle design and is approximately illustrated inFIG. 9b . Typically, the conical spray patterns of the instantdisclosure are hollow rings of the mixture sprayed from the spray nozzle(20). It is contemplated that the mixture may be sprayed at any sprayangle or within any range of spray angles within the ranges set forthabove.

In one embodiment, the instant mixture is sprayed with a spray nozzlethat is commercially available from Spraying Systems Co. of Wheaton,Ill. having a part number of 5050. In this embodiment, the spray nozzleis rated for flow of 5 gallons of water per minute water at 40 psi,produces a control spray angle of approximately 50°, produces a sprayangle of the instant mixture of about 31°, and produces a spray width ofthe instant mixture of approximately 17 inches when measured at adistance (D) of about 30 inches from the spray nozzle. In anotherembodiment, the instant mixture is sprayed with a spray nozzle that iscommercially available from Spraying Systems Co having a part number of5070. In this embodiment, the spray nozzle is rated for flow of 5gallons of water per minute water at 40 psi, produces a control sprayangle of approximately 70°, produces a spray angle of the instantmixture of about 35°, and produces a spray width of the instant mixtureof approximately 19 inches when measured at a distance (D) of about 30inches from the spray nozzle. In yet another embodiment, the instantmixture is sprayed with a spray nozzle that is commercially availablefrom Spraying Systems Co. having a part number of 5030. In thisembodiment, the spray nozzle is rated for flow of 5 gallons of water perminute water at 40 psi, produces a control spray angle of approximately30°, produces a spray angle of the instant mixture of about 43°, andproduces a spray width of the instant mixture of approximately 24 incheswhen measured at a distance (D) of about 30 inches from the spraynozzle. In still another embodiment, the instant mixture is sprayed witha spray nozzle that is commercially available from Spraying Systems Co.having a part number of 5015. In this embodiment, the spray nozzle israted for flow of 5 gallons of water per minute water at 40 psi,produces a control spray angle of approximately 15°, produces a sprayangle of the instant mixture of about 47°, and produces a spray width ofthe instant mixture of approximately 26 inches when measured at adistance (D) of about 30 inches from the spray nozzle.

The spray pattern produced by the spray nozzle, whether flat or conical,is not limited to the above widths and may have different widths asdesired by one of skill in the art. As first described above, the actualspray widths measured when spraying the instant mixture through thespray nozzle (20) may be different from the control spray widthsdescribed herein due to the viscosity of the mixture as compared to theviscosity of the water standard. In one embodiment, the spray width (W)is related to the spray angle (α) and the spray pressure. However, thespray width (W) may not necessarily be related to the spray angle (α)and/or the spray pressure. The following table sets forth someexemplary, but non-limiting, control spray widths (W) that may beutilized in this disclosure. The following control spray widths aremeasured at a pressure of 40 psi using water as a standard.

Control Spray Angle α (°) Distance (D) From Spray nozzle (inches) Usingat Which Control Spray Width Water as a Measured Using Water as aStandard Standard 6″ 8″ 10″ 12″ 15″ 18″ Control Spray Widths (inches) 151.6 2.1 2.6 3.2 3.9 4.7 25 2.7 3.5 4.4 5.3 6.6 8.0 40 4.4 5.8 7.3 8.710.9 13.1 65 7.6 10.2 12.7 15.3 19.2 22.9 80 10.1 13.4 16.8 20.2 25.230.3 110 17.1 22.8 28.5 34.3 42.8 51.4

In addition to the method, a polyurethane spraying system (hereinafterreferred to as the “system”) is also provided. A non-limiting schematicof one embodiment the system is set forth in FIG. 12 wherein (A) is oneembodiment of a proportioner or mixer of this disclosure, (B) is aheated hose, (C) is a heated whip hose, (D) is a fusion spray gun, (E)is an air line, (F) is a feed pump, (G) is a fluid supply line, and (H)is a fluid inlet. The system is used to minimize emissions of thepolyisocyanate while spraying the mixture of the polyisocyanate and theresin composition onto the surface (S). The system includes a firstreactant supply tank that includes the resin composition and a secondreactant supply tank that includes the polyisocyanate. The first andsecond reactant supply tanks may be any known in the art such as totes,drums, and tanks, and may be any size and shape. Typically, the firstand second reactant supply tanks have a capacity of from 150 pounds to40,000 pounds. The first and second reactant supply tanks are typicallytransportable and light-weight such that they can be easily utilized ina variety of applications. Alternatively, the first and second reactantsupply tanks may be permanent and not movable. It is also contemplatedthat the system may include more than two reactant supply tanks. Forexample, third and fourth, (or more) reactant supply tanks may beutilized and may include additional polyisocyanates, polyols, oradditives, in addition to those described above. Typically, the contentsof both the first and second reactant supply tanks have a viscosity ofless than or equal to about 1200 cps and more typically less than about600 cps when measured at 70° F.

The system also includes a non-gaseous pump, i.e., a pump that does notutilize a gas to pump, push, or move the contents of the first andsecond reactant supply tanks. The non-gaseous pump is not particularlylimited and may be further defined as a piston pump, an opposed pistonmetering pump, a double acting piston pump, a pneumatic pump, a directlift pump, a gravity pump, a hydraulic pump, a positive displacementpump such as a gear pump, a progressive cavity pump, a roots-type pump,a peristaltic pump, a reciprocating-type pump, an impulse pump, ahydraulic ram pump, a velocity pump, a centrifugal pump, a radial flowpump, an axial flow pump, a mixed flow pump, an eductor-jet pump, asteam pump, a valveless pump, a rotary pump, a screw pump, a rotary gearpump, a diaphragm pump, a vane pump, etc.

Typically, the non-gaseous pump is in fluid communication with both thefirst and second reactant supply tanks and may supply a pressure of from100-500 psi, of from about 200 to 250 psi, of from about 250 to 500 psi,or of about 235 psi. In one embodiment, the system includes a pumpingmetering unit that can be operated at a pressure of about 200 to 250psi.

The system also includes a mixing apparatus (or more than one mixingapparatus), e.g. a proportioner, that is coupled with the first andsecond reactant supply tanks and coupled with the non-gaseous pump formixing the resin composition and the polyisocyanate prior to spraying.The mixing apparatus is typically coupled and in fluid communicationwith the first and second reactant supply tanks via connecting meanssuch as hoses, valves, and/or fluid lines. In one embodiment, theconnecting means is heated to a temperature of from 75° F. to 90° F. Themixing apparatus is also typically coupled with the non-gaseous pump viaconnecting means that may be the same or different from the connectingmeans described above.

In an alternative embodiment, the one or more mixing apparatus iscoupled and in fluid connection with the first and second reactantsupply tanks through a ratio control device. The ratio control devicemay be further defined as a gear box that is used to monitor and controlthe ratio of the contents of the first and second reactant supply tanks.The one or more mixing apparatus may also be coupled and in fluidconnection with the first and second reactant supply tanks through aflow controller. The flow controller and the ratio control device may becoupled and in fluid connection with each other. Typically, the flowcontroller controls a flow of the contents of the first and secondreactant supply tanks.

The mixing apparatus may be further defined as a plural componentproportioner, as is known in the art. Suitable, but non-limiting,examples of mixing apparatuses are commercially available from GracoInc. of Minneapolis, Minn., under the trade names of Reactor E-XP1 andE-XP2, Reactor E-10, Reactor H-XP2 and H-XP3, Reactor H-VR, GuardianA-6, Reactor E-20 and E-30, Reactor E-10, Reactor H-25, H-40 and H-50,Reactor A-20, Guardian A-5, Gusmer H-20/35, Gusmer-Decker Proportioners.Additional non-limiting examples of mixing apparatuses, and more generalspray-foam systems that can utilize one or more embodiments of theinstant disclosure, include SPRAYTITE 178, ENERTITE NM, ENERTITE US,SPRAYTITE 180, SPRAYTITE 158, and SPRAYTITE 158LDWREV, as set forth inthe art. In fact, the mixing apparatuses and general spray-foams systemswhich may utilize one or more embodiments of the instant disclosure arenot particularly limited. The non-gaseous pump of this disclosure may befurther defined as a pump of one or more of these apparatuses. Thecomponents, designs, orientations, operations, and specifications ofeach of the aforementioned mixing apparatuses, and the non-gaseous pumpsincluded therein, are expressly contemplated as suitable for use in thisdisclosure and as optional components in this disclosure. Individualdescriptions of each of these components are not included herein for thesake of brevity but nonetheless remain as contemplated non-limitingoptions for use in this disclosure.

In addition, the system includes the spray nozzle (20), which may be asdescribed above and/or below. The spray nozzle (20) is coupled with themixing apparatus and minimizes emissions of the polyisocyanate whilespraying the mixture onto the surface (S). The spray nozzle (20) istypically further defined as a cone nozzle or a fan nozzle. Particularlysuitable cone nozzles include, but are not limited to, full conenozzles, hollow cone nozzles, and combinations thereof. Particularlysuitable fan nozzles include, but are not limited to, flat fan nozzles,flooding fan nozzles, and combinations thereof. Of course, any spraynozzle known in the art may be used with the system so long as themixture is sprayed as described above and the spray nozzle minimizes theemissions of the polyisocyanate upon spraying.

In addition to the description above, the spray nozzle (20) typicallyincludes a nozzle body (22) having a longitudinal axis (L) and upstreamand downstream ends (24, 26) opposite each other, as shown in FIGS. 1-7.The spray nozzle (20) also typically has a passage defined by the nozzlebody (22) and in fluid communication with the upstream and downstreamends (24, 26) along the longitudinal axis (L) for receiving the mixture.

The spray nozzle (20) also typically has a spraying orifice (28) definedby the nozzle body (22) and disposed at the downstream end (26) of thenozzle body (22) transverse to the longitudinal axis (L) for sprayingthe mixture, as also shown in FIGS. 1-7. The spraying orifice (28) maybe of any size and shape but typically is circular and has a radius (r)of from about 0.01 to about 0.25 inches.

In one embodiment, the upstream end (24) of the spray nozzle (20) isthreaded such that the spray nozzle (20) may be a “male” or “female”nozzle, as is known in the art. Examples of “male” nozzles areillustrated in FIGS. 1a, 1b, 3a, 3b , 5, 6 a-6 c, and 7 a-7 c. Examplesof “female” nozzles are illustrated in FIGS. 2a, 2b, 4a, and 4b . Inanother embodiment, the nozzle body (22) has an integrally formed flange(30) extending radially therefrom, as shown in FIGS. 1-7. The integrallyformed flange (30) may be disposed between the threaded upstream end(24) and the downstream end (26) for supporting the nozzle body (22) andshown in FIGS. 1a, 1b, 3a, 3b , 5, 6 a-6 c, and 7 a-7 c. Typically, theflange (30) has a plurality of flats (32) disposed transverse to thelongitudinal axis (L) to allow for threaded engagement of the threadedupstream end (24) to a supply line that provides the mixture of thepolyisocyanate and the resin composition to the spray nozzle (20) asshown in FIGS. 1-7. The spray nozzle (20) may also include an insert,such as a stabilizer vane, (not shown in the Figures) to reduceturbulence of the mixture and improve spray pattern efficiency.

In addition, the system may also include any other typical componentssuch as air-bleed valves, water-flushes, air blow offs, filters, and thelike. These components may be selected by one of skill in the art andused at any appropriate point in the system. In one embodiment, thesystem includes a series of regulators and valves. The elements of thespray system can be “coupled” to each other by any means known in theart including piping, tubing, with supply lines, and the like, asselected by one of skill in the art.

EXAMPLES

A mixture (Mixture 1) of a polyisocyanate and a resin composition ofthis disclosure is formed and is sprayed onto a surface according to themethod of this disclosure. A comparative mixture (Comparative Mixture 1)including the same polyisocyanate and a comparative resin composition isalso formed and sprayed onto a surface but not according to thisdisclosure. During spraying, concentrations (i.e., emissions) of thepolyisocyanate in the air are measured according to the NIOSH 5521Impingement Method and reported below.

Formation and Spraying of Mixture 1:

The chemical composition of Mixture 1 is as follows:

Polyisocyanate:

The Polyisocyanate is methylene diphenyl diisocyanate (MDI) that iscommercially available from BASF Corporation. The Polyisocyanate iscombined with the Resin Composition described below at an IsocyanateIndex of about 115.

Resin Composition:

The Resin Composition includes the following wherein the parts by weightare per 100 parts by weight of the Resin Composition:

10 parts by weight of Blowing Agent which is1,1,1,3,3-pentafluoropropane (HFC R-245fa) that is commerciallyavailable from Honeywell under the trade name of Enovate®;

27.25 parts by weight of a Mannich Polyol which is a polyether polyolhaving a nominal functionality of approximately four, a hydroxyl numberof 425 mg KOH/g, and a 20% ethylene oxide cap, and that is commerciallyavailable from Carpenter Co. under the trade name of Carpol® MX-425;

33.45 parts by weight of Additional Polyol 1 which is an aromaticpolyester polyol having a hydroxyl number of 235-265 mg KOH/g andcommercially available from Oxid, Inc. of Houston, Tex. under the tradename Terol® 250;

3 parts by weight of Additional Polyol 2 which is a glycerine/sucroseinitiated polyether polyol having a nominal hydroxyl number of 280 mgKOH/g and a nominal functionality of 7 and is commercially availablefrom Carpenter Co. under the trade name Carpol® GSP-280;

0.3 parts by weight of Catalyst 1 which is dimethylethanolamine and iscommercially available from Air Products & Chemicals, Inc. under thetrade name of DABCO® DMEA;

3 grams of Catalyst 2 which is a solution of1,4-Diazabicyclo[2.2.2]octane that is commercially available from AirProducts & Chemicals, Inc. under the trade name of DABCO® 33LV;

1.5 parts by weight of Catalyst 3 which is a blow catalyst that ispolyoxypropylenediamine that is commercially available from HuntsmanCorporation under the trade name of D-230;

0.5 parts by weight of Catalyst 4 which is a tin catalyst that iscommercially available from Air Products & Chemicals, Inc. under thetrade name of DABCO® T;

1 part by weight of Surfactant which is a silicone surfactant that iscommercially available from Air Products & Chemicals, Inc. under thetrade name of DABCO® DC 193;

10 parts by weight of Additive 1 which is a flame retardant that istriethylphosphate is commercially available from Shanghia Soar Roc underthe trade name of TEP;

8 parts by weight of Additive 2 which is a flame retardant that iscommercially available from Great Lakes Chemical under the trade name ofPHT 4-Diol;

2 parts by weight of deionized water.

After formation, Mixture 1 is sprayed onto a cardboard surface using themethod of this disclosure and a flat fan spray nozzle that iscommercially available from Spraying Systems Co. under the trade nameVeeJet® 4U-4040. This sample is sprayed through the flat fan spraynozzle at a pressure of 250 psi, at a 40 degree spray angle, at atemperature of about 85° F., and at a rate of approximately 9lbs/minute, using a Graco Fusion type impingement spray gun that is airpurged with a AR4242 Module, as known in the art.

More specifically, Mixture 1 is sprayed onto the cardboard surface forapproximately 15 minutes. Throughout the 15 minutes, concentrations(i.e., emissions) of the polyisocyanate in the air are measured at twodifferent distance intervals (Distances 1 and 2). The concentrations aremeasured according to the NIOSH 5521 Impingement Method and are reportedas an average in parts per billion of the polyisocyanate in the air. Theconcentrations are set forth in Table 1 below.

For the instant Examples, a modification of the OSHA method 47, usingimpingers backed up with 13 mm filters, is used and allows greatersensitivity and capture of the aerosol, both in the impinger and filter,for subsequent analysis of the monomer and three ring oligomer of MDI.

Formation and Spraying of Comparative Mixture 1:

One sample of the Comparative Mixture is also sprayed onto a cardboardsurface but is sprayed using a Graco Fusion type impingement spray gunthat is air purged with a AR4242 Module, as known in the art. Thesamples are sprayed using the standard spray foam applicationconfiguration at a pressure of 1200 psi, at a temperature of about 130°F., at a rate of approximately 11 lbs/minute, and for a time of about 15minutes. A spray nozzle of this disclosure is not utilized whatsoever inthe spraying of Comparative Mixture 1.

Throughout the 15 minutes, concentrations (i.e., emissions) of thepolyisocyanate in the air are measured at two different distanceintervals (Distances 1 and 2). The concentrations are measured accordingto the NIOSH 5521 Impingement Method and are reported as an average inparts per billion of the polyisocyanate in the air. The concentrationsare set forth in Table 1 below and in the bar graph of FIG. 13.

TABLE 1 Overall Distance 1 Distance 2 Emission Mixture 1 23.3 7.5 30.8Comparative Mixture 1 59 4.17 63.17 Total Percent Reduction in — — −49%Emissions

The reported emissions at Distance 1 are determined approximately 2.5feet measured perpendicularly from the cardboard surface at a height ofapproximately 6 feet from ground. The inlet of the monitoring equipmentwas placed at shoulder height of the individual spraying. In the bargraph of FIG. 13, this distance can alternatively be described as“Personal” distance.

The reported emissions at Distance 2 are determined approximately 10feet measured perpendicularly from the cardboard surface at a height of4 feet from the ground. In the bar graph of FIG. 13, this distance canalternatively be described as “Area” distance.

The “Overall Emission” is calculated by summing the emissions fromDistances 1 and 2, e.g. from the “Personal” and “Area” distances of FIG.13.

The results set forth above indicate that use of the system and methodof this disclosure significantly decreases emissions and theconcentration of the polyisocyanate in the air. The results alsoindicate that the mixture can be sprayed using this disclosure in closedand/or non-ventilated environments with minimized risk of over exposureto the polyisocyanate. The results further indicate that this methodminimizes a need to use respirators and protective equipment whenspraying the mixture.

One or more of the values described above may vary by ±5%, ±10%, ±15%,±20%, ±25%, etc. so long as the variance remains within the scope of thedisclosure. Unexpected results may be obtained from each member of aMarkush group independent from all other members. Each member may berelied upon individually and or in combination and provides adequatesupport for specific embodiments within the scope of the appendedclaims. The subject matter of all combinations of independent anddependent claims, both singly and multiply dependent, is hereinexpressly contemplated. The disclosure is illustrative including wordsof description rather than of limitation. Many modifications andvariations of the present disclosure are possible in light of the aboveteachings, and the disclosure may be practiced otherwise than asspecifically described herein.

What is claimed is:
 1. A polyurethane spraying system used to minimizeemissions of a polyisocyanate while spraying a mixture of apolyisocyanate and a resin composition onto a surface at a rate of 5 to30 lbs/min, said system comprising: A. a first reactant supply tankcomprising the resin composition having a hydroxyl content of at least400 mg KOH/g and comprising; (i) a blowing agent that is a liquid atroom temperature under a pressure greater than atmospheric pressure;(ii) a first polyol selected from the group of a Mannich polyol, anautocatalytic polyol, and combinations thereof; (iii) at least oneadditional polyol other than the first polyol; (iv) an optionalcatalyst; (v) an optional surfactant, and (vi) optionally water, whereinsaid resin composition has no other blowing agents; B. a second reactantsupply tank comprising the polyisocyanate; C. a non-gaseous pump that iscoupled with said first and second reactant supply tanks; D. a mixingapparatus that is coupled with said first and second reactant supplytanks for mixing the resin composition and the polyisocyanate prior tospraying; E. a spray nozzle that is coupled with said mixing apparatusand that produces less than 50 parts of the polyisocyanate per onebillion parts of air according to the National Institute forOccupational Safety and Health 5521 Impingement Method while sprayingthe mixture onto the surface to form a polyurethane foam, said spraynozzle comprising; (i) a nozzle body having a longitudinal axis,upstream and downstream ends opposite each other, and a passage definedby said nozzle body and in fluid communication with said upstream anddownstream ends along said longitudinal axis for receiving the mixture;and (ii) a circular spraying orifice having a radius of from 0.01 to0.25 inches and defined by said nozzle body and disposed at saiddownstream end of said nozzle body transverse to said longitudinal axisfor spraying the mixture at a spray angle corresponding to a controlspray angle of from 15 to 125 degrees measured at a pressure of from 10to 40 psi using water as a standard, and wherein said spray nozzleproduces a flat spray pattern.
 2. A polyurethane spray system as setforth in claim 1 wherein the polyurethane foam has a closed cell contentof at least 90 percent.
 3. A polyurethane spray system as set forth inclaim 1 wherein the polyurethane foam is further defined as an open cellfoam.
 4. A polyurethane spraying system as set forth in claim 1 whereinsaid non-gaseous pump is further defined as a piston pump.
 5. Apolyurethane spraying system as set forth in claim 4 wherein said firstand second reactant supply tanks are pressurized to a pressure of fromabout 200 to about 250 psi.
 6. A polyurethane spraying system as setforth in claim 5 wherein said mixing apparatus is coupled with saidfirst and second reactant supply tanks via a connecting means that isheated to a temperature of from 90° F. to 100° F.
 7. A polyurethanespraying system as set forth in claim 5 wherein said mixing apparatus iscoupled with said first and second reactant supply tanks via aconnecting means that is heated to a temperature of from 125° F. to 135°F.
 8. A polyurethane spraying system as set forth in claim 1 wherein thespray angle is further defined as corresponding to a control spray angleof from 15 to 120 degrees measured at a pressure of 40 psi using wateras a standard, wherein the flat spray pattern is substantially planar,and wherein the flat spray pattern has a spray width corresponding to acontrol spray width of from 2 to 30 inches measured at a distance ofabout 10 inches from the spray nozzle using water as the standard.
 9. Apolyurethane spraying system as set forth in claim 8 wherein the sprayangle is further defined as corresponding to a control spray angle of15, 25, 40, 50, 65, 80, 95, 110, or 120 degrees measured at a pressureof 40 psi using water as a standard.
 10. A polyurethane spraying systemas set forth in claim 1 wherein the spray angle is further defined ascorresponding to a control spray angle of from 15 to 125 degreesmeasured at a pressure of 10 psi using water as a standard.
 11. Apolyurethane spraying system as set forth in claim 10 wherein the sprayangle is further defined as corresponding to a control spray angle offrom 50 to 80 degrees measured at a pressure of 10 psi using water as astandard.
 12. A polyurethane spraying system as set forth in claim 10wherein the spray angle is further defined as corresponding to a controlspray angle of from 120 to 125 degrees measured at a pressure of 10 psiusing water as a standard.
 13. A polyurethane spraying system as setforth in claim 1 wherein said spray nozzle that is coupled with saidmixing apparatus produces less than 25 parts of the polyisocyanate perone billion parts of air according to the National Institute forOccupational Safety and Health 5521 Impingement Method while measured athorizontal distance of about 2.5 feet from a surface and at a verticaldistance of about 6 feet from the ground.
 14. A polyurethane sprayingsystem as set forth in claim 13 wherein said spray nozzle that iscoupled with said mixing apparatus produces less than 8 parts of thepolyisocyanate per one billion parts of air according to the NationalInstitute for Occupational Safety and Health 5521 Impingement Methodwhile measured at horizontal distance of about 10 feet from a surfaceand at a vertical distance of about 4 feet from the ground.
 15. Apolyurethane spraying system used to minimize emissions of apolyisocyanate while spraying a mixture of a polyisocyanate and a resincomposition onto a surface at a rate of 5 to 30 lbs/min, said systemcomprising: A. a first reactant supply tank pressurized to a pressure offrom about 200 to about 250 psi and comprising the resin compositionhaving a hydroxyl content of at least 400 mg KOH/g and comprising; (i) ablowing agent that is a liquid at room temperature under a pressuregreater than atmospheric pressure; (ii) a first polyol selected from thegroup of a Mannich polyol, an autocatalytic polyol, and combinationsthereof; (iii) at least one additional polyol other than the firstpolyol; (iv) an optional catalyst; (v) an optional surfactant, and (vi)optionally water, wherein said resin composition has no other blowingagents; B. a second reactant supply tank pressurized to a pressure offrom about 200 to about 250 psi and comprising the polyisocyanate; C. apiston pump that is coupled with said first and second reactant supplytanks; D. a mixing apparatus that is coupled with said first and secondreactant supply tanks for mixing the resin composition and thepolyisocyanate prior to spraying; E. a spray nozzle that is coupled withsaid mixing apparatus, said spray nozzle comprising; (i) a nozzle bodyhaving a longitudinal axis, upstream and downstream ends opposite eachother, and a passage defined by said nozzle body and in fluidcommunication with said upstream and downstream ends along saidlongitudinal axis for receiving the mixture; and (ii) a circularspraying orifice having a radius of from 0.01 to 0.25 inches and definedby said nozzle body and disposed at said downstream end of said nozzlebody transverse to said longitudinal axis for spraying the mixture at aspray angle corresponding to a control spray angle of from 15 to 125degrees measured at a pressure of from 10 to 40 psi using water as astandard, and wherein said spray nozzle that is coupled with said mixingapparatus produces a flat spray pattern and less than 8 parts of thepolyisocyanate per one billion parts of air according to the NationalInstitute for Occupational Safety and Health 5521 Impingement Methodwhile measured at horizontal distance of about 10 feet from a surfaceand at a vertical distance of about 4 feet from the ground.
 16. Apolyurethane spraying system as set forth in claim 15 wherein the sprayangle is further defined as corresponding to a control spray angle offrom 15 to 125 degrees measured at a pressure of 10 psi using water as astandard.
 17. A polyurethane spraying system as set forth in claim 16wherein the spray angle is further defined as corresponding to a controlspray angle of from 50 to 80 degrees measured at a pressure of 10 psiusing water as a standard.
 18. A polyurethane spraying system as setforth in claim 16 wherein the spray angle is further defined ascorresponding to a control spray angle of from 120 to 125 degreesmeasured at a pressure of 10 psi using water as a standard.
 19. Apolyurethane spraying system as set forth in claim 15 wherein saidmixing apparatus is coupled with said first and second reactant supplytanks via a connecting means that is heated to a temperature of from 90°F. to 100° F.
 20. A polyurethane spraying system as set forth in claim15 wherein said mixing apparatus is coupled with said first and secondreactant supply tanks via a connecting means that is heated to atemperature of from 125° F. to 135° F.
 21. A polyurethane sprayingsystem as set forth in claim 1 wherein said spray nozzle is rated forflow of 5 gallons of water per minute water at 40 psi, produces acontrol spray angle of approximately 50°, produces a spray angle of saidmixture of about 31°, and produces a spray width of said mixture ofapproximately 17 inches when measured at a distance (D) of about 30inches from said spray nozzle.